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Title: Three-dimensional framework of uranium-centered polyhedra with non-intersecting channels in the uranyl oxy-vanadates A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O (A=Li, Na)

Abstract

The uranyl vanadates A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O (A=Li, Na) have been synthesized by solid-state reaction and the structure of the Li compound was solved from single-crystal X-ray diffraction. The crystal structure is built from {sub {infinity}}{sup 1}[UO{sub 5}]{sup 4{sup -}} chains of edge-shared U(2)O{sub 7} pentagonal bipyramids alternatively parallel to a-vector- and b-vector-axis and further connected together to form a three-dimensional (3-D) arrangement. The perpendicular chains are hung on both sides of a sheet {sub {infinity}}{sup 2}[(UO{sub 2})(VO{sub 4}){sub 2}]{sup 4-} parallel to (001), formed by U(1)O{sub 6} square bipyramids connected by VO{sub 4} tetrahedra, and derived from the autunite-type sheet. The resulting 3-D framework creates non-intersecting channels running down the a-vector- and b-vector-axis formed by empty face-shared oxygen octahedra, the Li{sup +} ions are displaced from the center of the channels and occupy the middle of one edge of the common face. The peculiar position of the Li{sup +} ion together with the full occupancy explain the low conductivity of Li{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O compared with that of Na(UO{sub 2}){sub 4}(VO{sub 4}){sub 3} containing the same type of channels half occupied by Na{sup +} ions in the octahedral sites. Crystallographic data for Li{sub 2}(UO{sub 2}){submore » 3}(VO{sub 4}){sub 2}O: tetragonal, space group I41/amd, a=7.3303(5)A, c=24.653(3)A, V=1324.7(2)A{sup 3}, Z=4, {rho}{sub mes}=5.32(2)g/cm{sup 3}, {rho}{sub cal}=5.36(3)g/cm{sup 3}, full-matrix least-squares refinement basis on F{sup 2} yielded, R{sub 1}=0.032, wR{sub 2}=0.085 for 37 refined parameters with 364 independent reflections with I>=2{sigma}(I)« less

Authors:
 [1];  [2];  [2];  [2]
  1. Unite de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, ENSCL-USTL, B.P. 90108, 59652 Villeneuve d'Ascq Cedex (France), E-mail: said.obbade@ensc-lille.fr
  2. Unite de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, ENSCL-USTL, B.P. 90108, 59652 Villeneuve d'Ascq Cedex (France)
Publication Date:
OSTI Identifier:
21015723
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2006.12.014; PII: S0022-4596(06)00647-5; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CRYSTALLOGRAPHY; LEAST SQUARE FIT; LITHIUM COMPOUNDS; LITHIUM IONS; MONOCRYSTALS; SODIUM COMPOUNDS; SODIUM IONS; SPACE GROUPS; SYNTHESIS; TETRAGONAL LATTICES; URANYL COMPOUNDS; VANADATES; X-RAY DIFFRACTION

Citation Formats

Obbade, S., Duvieubourg, L., Dion, C., and Abraham, F. Three-dimensional framework of uranium-centered polyhedra with non-intersecting channels in the uranyl oxy-vanadates A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O (A=Li, Na). United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.12.014.
Obbade, S., Duvieubourg, L., Dion, C., & Abraham, F. Three-dimensional framework of uranium-centered polyhedra with non-intersecting channels in the uranyl oxy-vanadates A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O (A=Li, Na). United States. doi:10.1016/j.jssc.2006.12.014.
Obbade, S., Duvieubourg, L., Dion, C., and Abraham, F. Thu . "Three-dimensional framework of uranium-centered polyhedra with non-intersecting channels in the uranyl oxy-vanadates A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O (A=Li, Na)". United States. doi:10.1016/j.jssc.2006.12.014.
@article{osti_21015723,
title = {Three-dimensional framework of uranium-centered polyhedra with non-intersecting channels in the uranyl oxy-vanadates A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O (A=Li, Na)},
author = {Obbade, S. and Duvieubourg, L. and Dion, C. and Abraham, F.},
abstractNote = {The uranyl vanadates A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O (A=Li, Na) have been synthesized by solid-state reaction and the structure of the Li compound was solved from single-crystal X-ray diffraction. The crystal structure is built from {sub {infinity}}{sup 1}[UO{sub 5}]{sup 4{sup -}} chains of edge-shared U(2)O{sub 7} pentagonal bipyramids alternatively parallel to a-vector- and b-vector-axis and further connected together to form a three-dimensional (3-D) arrangement. The perpendicular chains are hung on both sides of a sheet {sub {infinity}}{sup 2}[(UO{sub 2})(VO{sub 4}){sub 2}]{sup 4-} parallel to (001), formed by U(1)O{sub 6} square bipyramids connected by VO{sub 4} tetrahedra, and derived from the autunite-type sheet. The resulting 3-D framework creates non-intersecting channels running down the a-vector- and b-vector-axis formed by empty face-shared oxygen octahedra, the Li{sup +} ions are displaced from the center of the channels and occupy the middle of one edge of the common face. The peculiar position of the Li{sup +} ion together with the full occupancy explain the low conductivity of Li{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O compared with that of Na(UO{sub 2}){sub 4}(VO{sub 4}){sub 3} containing the same type of channels half occupied by Na{sup +} ions in the octahedral sites. Crystallographic data for Li{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O: tetragonal, space group I41/amd, a=7.3303(5)A, c=24.653(3)A, V=1324.7(2)A{sup 3}, Z=4, {rho}{sub mes}=5.32(2)g/cm{sup 3}, {rho}{sub cal}=5.36(3)g/cm{sup 3}, full-matrix least-squares refinement basis on F{sup 2} yielded, R{sub 1}=0.032, wR{sub 2}=0.085 for 37 refined parameters with 364 independent reflections with I>=2{sigma}(I)},
doi = {10.1016/j.jssc.2006.12.014},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 180,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}
  • New uranyl vanadates A{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O (M=Li (1), Na (2), Ag (3)) have been synthesized by solid-state reaction and their structures determined from single-crystal X-ray diffraction data for 1 and 3. The tetragonal structure results of an alternation of two types of sheets denoted S for {sub {infinity}}{sup 2}[UO{sub 2}(VO{sub 4}){sub 2}]{sup 4-} and D for {sub {infinity}}{sup 2}[(UO{sub 2}){sub 2}(VO{sub 4}){sub 3}]{sup 5-} built from UO{sub 6} square bipyramids and connected through VO{sub 4} tetrahedra to {sub {infinity}}{sup 1}[U(3)O{sub 5}-U(4)O{sub 5}]{sup 8-} infinite chains of edge-shared U(3)O{sub 7} and U(4)O{sub 7} pentagonal bipyramids alternatively parallel tomore » a- and b-axis to construct a three-dimensional uranyl vanadate arrangement. It is noticeable that similar {sub {infinity}}[UO{sub 5}]{sup 4-} chains are connected only by S-type sheets in A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O and by D-type sheets in A(UO{sub 2}){sub 4}(VO{sub 4}){sub 3}, thus A{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O appears as an intergrowth structure between the two previously reported series. The mobility of the monovalent ion in the mutually perpendicular channels created in the three-dimensional arrangement is correlated to the occupation rate of the sites and by the geometry of the different sites occupied by either Na, Ag or Li. Crystallographic data: 293 K, Bruker X8-APEX2 X-ray diffractometer equipped with a 4 K CCD detector, MoK{alpha}, {lambda}=0.71073 A, tetragonal symmetry, space group P4-bar m2, Z=1, full-matrix least-squares refinement on the basis of F{sup 2}; 1,a=7.2794(9) A, c=14.514(4) A, R1=0.021 and wR2=0.048 for 62 parameters with 782 independent reflections with I{>=}2{sigma}(I); 3, a=7.2373(3) A, c=14.7973(15) A, R1=0.041 and wR2=0.085 for 60 parameters with 1066 independent reflections with I{>=}2{sigma}(I). - Abstract: A view of the three-dimensional structure of Li{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O. Display Omitted.« less
  • Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 formore » 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.« less
  • Hydrothermal reaction of VCl{sub 4} with phosphorous acid H{sub 3}PO{sub 3}, in the presence of organoamines, yields oxovanadium (IV)-phosphite materials: [HN(Me)(CH{sub 2}CH{sub 2}){sub 2}N(Me)H][(VO){sub 4}(OH){sub 2}-(HPO{sub 3}){sub 4}] (1), [H{sub 2}N(CH{sub 2}CH{sub 2}){sub 2}NH{sub 2}][(VO){sub 3}(HPO{sub 3}){sub 4}-(H{sub 2}O){sub 2}] (2), and [VO(HPO{sub 3})H{sub 2}O] (3). The framework structure of 3 is presented. 32 refs., 3 figs.
  • Four new Li uranyl phosphates and arsenates have been prepared by high-temperature solid-state reactions: {alpha}-Li[(UO{sub 2})(PO{sub 4})] (1), {alpha}-Li[(UO{sub 2})(AsO{sub 4})] (2), {beta}-Li[(UO{sub 2})(AsO{sub 4})] (3) and Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] (4). The structures of the compounds have been solved by direct methods: 1-triclinic, P1-bar, a=5.0271(1) A, b=9.8799(2) A, c=10.8920(2) A, {alpha}=108.282(9){sup o}, {beta}=102.993(8){sup o}, {gamma}=104.13(1){sup o}, V=470.69(2) A{sup 3}, Z=4, R{sub 1}=0.0415 for 2786 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 2-triclinic, P1-bar, a=5.129(2) A, b=10.105(3) A, c=11.080(3) A, {alpha}=107.70(2){sup o}, {beta}=102.53(3){sup o}, {gamma}=104.74(3){sup o}, V=501.4(3) A{sup 3}, Z=4, R{sub 1}=0.055 for 1431 unique reflections with |F{submore » 0}|{>=}4{sigma}{sub F}; 3-triclinic, P1-bar, a=5.051(1) A, b=5.303(1) A, c=10.101(1) A, {alpha}=90.31(1){sup o}, {beta}=97.49(1){sup o}, {gamma}=105.08(1){sup o}, V=258.80(8) A{sup 3}, Z=2, R{sub 1}=0.0339 for 2055 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 4-triclinic, P1-bar, a=5.312(1) A, b=6.696(1) A, c=12.542(1) A, {alpha}=94.532(9){sup o}, {beta}=99.059(8){sup o}, {gamma}=110.189(7){sup o}, V=409.17(10) A{sup 3}, Z=2, R{sub 1}=0.0565 for 1355 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}. The structures of all four compounds are based upon 3-D frameworks of U and T polyhedra (T=P, As). Phases 1 and 2 are isostructural and consist of U{sub 2}O{sub 12} dimers and UO{sub 6} square bipyramids linked by single TO{sub 4} tetrahedra. The structure of 3 consists of 3-D framework of corner-sharing UO{sub 6} bipyramids and AsO{sub 4} tetrahedra. In the structure of 4, the framework is composed of U{sub 2}O{sub 12} dimers, UO{sub 6} bipyramids and P{sub 2}O{sub 7} dimers. In all the compounds, Li{sup +} cations reside in framework cavities. The topologies of the 3-D frameworks can be described as derivatives of the PtS (cooperite) network. - Graphical abstract: Polyhedral and topological presentation of Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] crystal structure.« less
  • Although thiolate ligands have been used to separate heavy metal ions from dilute solution, typical uranophilic ligands not unexpectedly contain oxygen and/or nitrogen donors with few examples of thiolate types. In fact, structurally characterized compounds of the uranyl group with sulfur donor ligands in general are largely restricted to 1,1-dithio acid types and thioether and thione groups, with a single reported example of a thiolate type in the mercaptopyridine N-oxide complex [UO{sub 2}(ONC{sub 5}H{sub 4}S){sub 2}(dmso)]. In the course of there investigations of the general coordination chemistry of thiopyrimidine and thiopyridine ligand types, the authors have prepared solutions of uranylmore » thiolate complexes which upon exposure to atmospheric oxygen yield crystalline materials that have been identified as the unusual binuclear thiolate-ligated peroxo complexes [HNEt{sub 3}]{sub 2}-[(UO{sub 2}){sub 2}(O{sub 2})(SC{sub 4}N{sub 2}H{sub 3}){sub 4}] (1) and [HNEt{sub 3}][H(UO{sub 2}){sub 2}(O{sub 2})(SC{sub 4}N{sub 2}H{sub 2}-Me){sub 4}]{center_dot}Me{sub 2}CO{center_dot}0.5Et{sub 3}N (2). While numerous peroxyuranates have been prepared, only oxygen hetero ligands have been previously employed, and despite the enhanced complex stability endowed by such coligands, structural characterization of peroxyuranates has remained elusive.« less